The present invention relates to silicon-containing polymers, also containing moieties of a 1,6-diazaspiro[4.4]nonane-2,7-dione, which are produced by the reaction of a primary amino-containing silicon compound and a spirodilactam precursor selected from 4-ketodicarboxylic acid compounds or spirodilactones of corresponding structure. In one modification, the spirodilactam precursor is a ketodicarboxylic acid compound having two carbon atoms between the central keto functionality and each carboxylic acid function. Expressed differently, the ketodiacid compound is a 4-oxoheptanedioic acid compound. Although a variety of such ketodiacid compounds are useful as precursors of the compounds of the invention, the preferred ketodiacid compounds have up to 30 carbon atoms inclusive and are represented by the formula ##STR1## wherein A independently is hydroxy, alkoxy, preferably lower alkoxy of up to 4 carbon atoms inclusive, or halo, preferably the middle halogens chloro and bromo, and Z independently is &gt;C(Z').sub.2 in which Z' independently is hydrogen; alkyl, preferably lower alkyl, of up to 4 carbon atoms inclusive, preferably methyl; halo, but preferably the lower halogens fluoro or chloro; aryl of up to 10 carbon atoms inclusive, preferably phenyl; or Z is such that two adjacent Z groups taken together form a ring system Z" of from 5 to 7 ring atoms, up to two of which are heteroatoms selected from nitrogen, oxygen or sulfur with the remainder of the ring atoms being carbon atoms, there being up to 15 carbon atoms inclusive in each Z", two of which serve to connect the carbon atoms connected by the adjacent Z groups. When the Z moieties are taken together to form the ring system Z", the ring is cycloaliphatic, aromatic or heterocyclic and is hydrocarbon containing only atoms of carbon and hydrogen besides any heteroatoms of the ring or is substituted hydrocarbon containing atoms such as halogen in the form of inert substituents.
In one embodiment employing a ketodiacid compound spirodilactam precursor, each Z moiety is acyclic or not part of a ring system and each Z is &gt;C(Z').sub.2 and the ketodiacid compound is an acyclic 4-oxoheptanedioic acid compound. In this embodiment, the spirodilactam precursor preferably has at least one hydrogen on each carbon atom adjacent to an acid functionality and is of the formula ##STR2## wherein A and Z' have the previously stated meanings. Such 4-oxoheptanedioic acid compounds include 4-oxoheptanedioic acid, dimethyl 4-oxoheptanedioate, 2,6-dimethyl-4-oxoheptanedioic acid, 2,3,5,6-tetramethyl-4-oxoheptanedioyl chloride, 3,5-diethyl-4-heptanedioic acid, dipropyl 2,6-di-n-butyl-4-oxoheptanedioate and 6-carbomethoxy-3,3,5,5-tetramethyl-4-oxohexanoic acid. The preferred ketodiacid compounds of the above formulas I and Ia are those wherein each Z' is hydrogen or methyl, preferably hydrogen, and each A is hydroxy or methoxy, preferably hydroxy. The compounds of the above formulas I and Ia are known compounds or are produced by known methods, particularly the method of U.S. Pat. No. 4,800,231. Conversion of the esters produced thereby to corresponding free acids or acid halides is by conventional methods as is the interconversion of acids, esters or acid halides of formulas I or Ia in general to obtain the 4-oxoheptanedioic acid compounds.
In a second embodiment of the ketodiacid compound spirodilactam precursor the 4-ketodiacid incorporates cyclic moieties between the keto group and each acid function, i.e., adjacent Z groups are Z". Such cyclic diacid compounds are represented by the formula ##STR3## wherein A and Z" have the previously stated meaning. Illustrative of these cyclic ketodiacids are di(2-carboxyphenyl) ketone, di(2-carbethoxyphenyl) ketone, di(2-carboxycyclohexyl) ketone, di(2-carbopropoxycyclo-4-pentenyl) ketone, di(2 chlorocarbonylphenyl) ketone, di(2-carboxypyridyl) ketone, 2-carboxyphenyl, N-methyl-3-carboxy-2-pyrryl ketone, di(3-carbomethoxy-2-morpholyl) ketone and di(3-carboxy-2-naphthyl) ketone. The preferred cyclic ketodicarboxylic acid compounds are those wherein each Z" is a ring system of 5 to 6 carbon atoms inclusive and up to 1 nitrogen heteroatom. Such dicyclic 4-ketodiacid compounds are known compounds or are produced by known methods such as the method described by U.S. Pat. No. 1,999,181 or by Cava et al, J. Am. Chem. Soc., 77, 6022 (1955).
In yet another embodiment of the ketodiacid compound spirodilactam precursor the ketodiacid incorporates one acyclic moiety and one cyclic moiety, e.g., the compounds represented by the formula ##STR4## wherein A, Z' and Z" have the previously stated meanings. Such ketodiacid compounds of one cyclic moiety are illustrated by 3-(2-carboxybenzoyl)propionic acid, 3-(2-carbomethoxy-2-pyridyloyl)-2-ethylproprionic acid, ethyl 3-(2-carbethoxybenzolyl)propionate and 3-(2-carboxy-4-methyl)butyrl chloride. The ketodiacid compounds of one cyclic moiety of formula III are known compounds or are produced by known methods.
In a second modification of the invention, the spirodilactam precursor is a 1,6-dioxospiro[4.4]nonane-2,7-dione wherein the ring system carbon atoms are unsubstituted (except for hydrogen) or substituted with other groups or form part of other cyclic moieties. One class of such spirodilactones is of the formula ##STR5## wherein Z has the previously stated meaning. In the embodiment of the spirodilactone spirodilactam precursor wherein each Z moiety is &gt;C(Z').sub.2, the precursor is represented by the formula ##STR6## wherein Z' has the previously stated meaning. Illustrative of such spirodilactones are 1,6-dioxaspiro[4.4]nonane-2,7-dione, 3,8-dimethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione, 3,4,8,9-tetramethyl-1,6-dioxaspiro[4.4]-nonane-2,7-dione, 4,9-diphenyl-1,6-dioxaspiro[4.4]nonane-2,7-dione, 3,4,8,9-tetrafluoro-1,6-dioxaspiro[4.4]nonane-2,7-dione and 3,3,4,4,8,8,9,9-octamethyl-1,6-dioxaspiro[4.4]nonane-2,7-dione. The preferred spirodilactones of formula VI are those where at least one Z' of each Z'-substituted carbon atom is hydrogen. Such compounds are known compounds or are produced by known methods such as the process of Pariza et al, Synthetic Communications, Vol. (13) 3, pp. 243-254 (1983.
In the embodiment of the spirodilactone spirodilactam precursor which incorporates a cyclic moiety as a portion of each of the two rings of the spirodilactone ring system, the spirodilactones are represented by the formula ##STR7## wherein Z" has the previously stated meaning. Typical compounds of this formula are 3,4,8,9-dibenzo-1,6-dioxaspiro[4.4]nonane-2,7-dione, 3,4,8,9-di(cyclopentano)-1,6-dioxaspiro[4.4]nonane-2,7-dione, 3,4,8,9-di(4-methylbenzo)-1,6,-dioxaspiro[4.4]nonane-2,7-dione and 3,4,8,9-di(pyridino)-1,6-dioxaspiro[4.4]nonane-2,7-dione. These compounds of formula VI are known compounds or are produced by known methods, for example, the process described by Cava et al, J. Am. Chem. Soc., 79 1706-1709 (1959) or the process described in U.S. Pat. No. 1,999,181.
In a third embodiment of the spirodilactone spirodilactam precursor one cyclic moiety is fused to one of the spiro rings and the other spiro ring is free of fused ring substituents. Such spirodilactones are represented by the formula ##STR8## wherein Z' and Z" have the previously stated meanings. Such spirodilactones with a ring fused to one but not both spiro rings are illustrated by 3-methyl-8,9-benzo-1,6-dioxaspiro[4.4]nonane-2,7-dione, 8,9-benzo-1,6-dioxaspiro[4.4]nonane-2,7-dione and 3,3,4,4-tetramethyl-8,9-morpholino-1,6-dioxaspiro[4.4]nonane-2,7-dione. Spirodilactones of the above formula VII are known compounds or are produced by known methods such as the dehydration of the corresponding ketodiacids. For example, 3-(2-carboxybenzoyl)propionic acid is dehydrated by application of heat to produce 3,4-benzo-1,6-dioxaspiro[4.4]nonane-2,7-dione.
In general, the preferred spirodilactone spirodilactam precursors are hydrocarbon except for the oxygen atoms of the lactone moieties, particularly those free from fused cyclic substituents (formula V) or which have a fused ring substituent on each spiro ring (formula VI). Specifically preferred spirodilactone spirodilactam precursors are 1,6-dioxaspiro[4.4]nonane-2,7-dione and 3,4,8,9-dibenzo-1,6-dioxaspiro[4.4]nonane-2,7-dione.
The polymeric products of the invention are produced by reacting the spirodilactam precursor with a primary amino-substituted silicon compound to produce a polymeric product having at least one moiety of 1,6-diazaspiro[4.4]nonane-2,7-dione with silicon-containing substituent on each spiro ring nitrogen atom. The primary amino-substituted silicon compounds useful in the preparation of the polymers of the invention are compounds having at least one primary amino hydrocarbyl silyl moiety wherein the remaining valences of the silicon are satisfied by alkyl of up to 10 carbon atoms inclusive, aryl of up to 10 carbon atoms inclusive, alkoxy of up to 10 carbon atoms inclusive or a hydrocarbon linking group of up to 10 carbon atoms inclusive to a second primary amino hydrocarbyl silyl moiety. Preferred aminohydrocarbyl silyl compounds are represented by the formula ##STR9## wherein R is alkylene or arylene of up to 10 carbon atoms inclusive, R' independently is of up to 10 carbon atoms inclusive and is alkyl, aryl or alkoxy, E is R' or ##STR10## wherein R and R' have the previously stated meaning. Illustrative of amino silyl compounds of the above formula VIII are 2-aminoethyltriethoxysilane, 4-aminophenyltripropoxysilane, 3-amino-5-methylphenylmethoxydiethoxysilane, (8-aminooctyl)-(2-aminoethyl) dimethoxysilane, 3-aminocyclohexyldimethylmethoxysilane, 6-aminohexyltricyclohexyloxysilane, 1,4-bis[(3-aminopropyl)dimethylsilyl]benzene, 1,6-bis[(2-aminoethyl)dimethoxysilyl]hexane, 4-aminobutyldiethylethoxysilane and 1,3-bis[(10-aminodecyl)dimethylsilyl]-4-methylbenzene. Particularly preferred as the aminohydrocarbyl silyl reactants are the compounds of the above formula VIII wherein E and each R' are alkoxy, especially methoxy, and R is alkylene of up to 6 carbon atoms inclusive or phenylene.
The aminohydrocarbyl silyl reactant and the spirodilactam precursor are contacted under reaction conditions to produce the polymer products of the invention. In one embodiment, the reaction takes place in liquid phase solution in the presence of an inert polar diluent such as N,N-dimethyl-2-pyrrolidone, dimethylsulfoxide or tetrahydrofuran. In an alternate embodiment, however, the reactants are contacted in the substantial absence of inert diluent by merely mixing the reactants and maintaining the resulting mixture under reaction conditions.
Typical reaction conditions include a reaction temperature of from about 100.degree. C. to about 190.degree. C., preferably from about 135.degree. C. to about 185.degree. C. The reaction pressure is that pressure sufficient to maintain the reaction mixture in the liquid phase. Such pressures are up to about 10 atmospheres but pressures from about 0.8 atmosphere to about 5 atmospheres are preferred. The molar ratio of aminohydrocarbyl silyl compound to spirodilactam precursor is suitably from about 5:1 to about 1:5. In the embodiment wherein E of the above formula VIII contains silicon, the preferred molar ratios of aminohydrocarbyl silyl compound to spirodilactam precursor are from about 2:1 to about 1:2. In the embodiment wherein E of the above formula VIII does not contain silicon, preferred molar ratios are from about 4:1 to about 1:2.
The contact of the reactants is facilitated by some means of agitation such as shaking or stirring. Subsequent to reaction, in the embodiment where reaction diluent is used, the polymer product is recovered upon removal of the diluent as by filtration or distillation. In the embodiment where the reaction is conducted in the absence of reaction diluent, the product is typically used as produced.
The product of the reaction of the aminohydrocarbyl silyl compound and the spirodilactam precursor will vary, depending in part upon the nature of the silyl compound. When the aminohydrocarbyl silyl compound is a compound of the above formula VIII wherein E is ##STR11## the polymer product is an alternating polymer wherein moieties derived from the aminohydrocarbyl silyl compound alternate with moieties of a spirodilactam. Upon reaction of either the ketodiacid spirodilactam precursor (formula I) or the spirodilactone spirodilactam precursor (formula IV) and the aminohydrocarbyl silyl compound of formula VIII wherein E is --R--Si(R').sub.2 --R--NH.sub.2, the products are represented by the repeating formula ##STR12## wherein Z, R and R' have the previously stated meaning. When the spirodilactam precursor of either formula I or formula IV is reacted with an aminohydrocarbyl silyl compound wherein E is R', a somewhat different type of polymer is produced of a structure not easily characterized. The polymeric products of this embodiment of the process of the invention are likely lightly crosslinked derivatives of a spirodilactam of the formula ##STR13## wherein R, R' and Z have the previously stated meanings. The crosslinking of this polymer is extended, i.e., the polymer is cured, by heating of the lightly-crosslinked initial polymer at a temperature of above about 190.degree. C. and preferably a temperature from about 195.degree. C. to about 225.degree. C. The more lightly crosslinked polymer is produced in one step by heating the aminohydrocarbyl silyl compound and spirodilactam precursor at a temperature above about 190.degree. C., but better results are produced if the reactants are heated at a reaction temperature below about 190.degree. C. and subsequently heated at the more elevated temperature. In this modification, isolation or characterization of the intermediate lightly crosslinked polymer is not required.
The polymers of the invention are thermoplastic in the case of the alternating polymers produced from aminohydrocarbyl silyl compounds of formula VIII wherein E is not R'. Such polymers are processed by methods conventional for thermoplastics into a variety of shaped articles, e.g., films, fibers and containers, which have established utility. In the case of the polymers produced from arylhydrocarbyl silyl compounds of the above formula VIII wherein E is R', the more highly crosslinked polymers produced by heating at the more elevated temperatures are thermoset polymers. Such polymers are processed by methods conventional for thermoset polymers and are useful in the production of circuit boards for electrical and electronic applications.